Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/04—Hybrid capacitors
  • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/74—Terminals, e.g. extensions of current collectors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0431—Cells with wound or folded electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0436—Small-sized flat cells or batteries for portable equipment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4242—Regeneration of electrolyte or reactants
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/44—Methods for charging or discharging
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
  • H01M4/382—Lithium
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
  • H01M6/5005—Auxiliary electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
  • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/44—Methods for charging or discharging
  • H01M10/446—Initial charging measures
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
  • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
  • H01M6/5044—Cells or batteries structurally combined with cell condition indicating means
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/13—Energy storage using capacitors
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/60—Other road transportation technologies with climate change mitigation effect
  • Y02T10/70—Energy storage systems for electromobility, e.g. batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49108—Electric battery cell making
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49108—Electric battery cell making
  • Y10T29/4911—Electric battery cell making including sealing

Definitions

• the present invention relates to a power storage device and a method for manufacturing the power storage device.
• the present invention relates to a power storage device capable of easily preventing unevenness in supporting lithium ions on a negative electrode and deformation of the negative electrode, and a method for manufacturing the same.
• a secondary battery using a conductive polymer, a transition metal oxide, or the like as a positive electrode and a lithium metal or a lithium alloy (hereinafter abbreviated as lithium metal or the like) as a negative electrode has been developed. Due to its high cost, it has been proposed as an alternative to Ni_Cd and lead batteries. However, when these secondary batteries are repeatedly charged and discharged, the capacity is greatly reduced due to deterioration of the positive electrode or the negative electrode, and there remains a problem in practical use.
• the deterioration of the negative electrode is accompanied by the formation of moss-like lithium crystals called dentite, and the repetition of charge and discharge eventually causes the dentite to penetrate through the separator, causing a short circuit inside the battery, In some cases, there was a problem in terms of safety, such as the battery exploding.
• the battery cell using the positive electrode L i C o 0 lithium-containing metal oxides such as 2 have been proposed, After the battery is assembled, it is charged by supplying lithium from the lithium-containing metal oxide of the positive electrode to the negative electrode, and then returned to the positive electrode by discharging.
• This is a so-called rocking chair type battery. Since only lithium ions are involved in charging and discharging without being used, they are called lithium ion secondary batteries and are distinguished from lithium batteries that use metal lithium. This battery features high voltage, high capacity, and high safety.
• Lithium-ion secondary batteries are mainly used for mobile phones and notebook computers, and further improvement in energy density is required.
• studies are being made on increasing the discharge capacity of each of the positive and negative electrodes, improving the charging and discharging efficiency, and improving the electrode density.
• the thickness and density of each electrode are determined so that the charge amount of the positive electrode and the charge amount of the negative electrode match. Therefore, the discharge capacity of the cell is determined by the lower charge / discharge efficiency of the positive or negative electrode. The higher the charge / discharge efficiency, the greater the cell capacity.
• PAS tin-based oxides and polyacene-based organic semiconductors
• PAS is obtained by heat-treating an aromatic polymer, and is described in Japanese Patent Publication No. 144442 / JP-B and Japanese Patent Publication No. 3-244204, etc.
• An insoluble and infusible substrate having a system skeleton structure is exemplified.
• a PAS having a specific surface area of 600 m 2 Zg or more by a BET method can be obtained by a method described in Japanese Patent Publication No. 3-240204 or the like.
• the present inventors achieved high capacity by preliminarily supporting lithium on the negative electrode PAS by the method described in Japanese Patent Application Laid-Open No. 8-79928 or the like.
• the conventional design could use only about 60% to 80% as the positive electrode capacity, but it could use 100% of the discharge capacity of both the positive and negative electrodes To increase the capacity.
• lithium-ion secondary batteries have been studied as high-capacity and powerful power sources, and have been put to practical use mainly as main power sources for notebook computers and mobile phones.
• mobile phones have become smaller and lighter, and lithium-ion secondary batteries used as main power sources have also been required to be thinner and lighter.
• the outer case for prismatic batteries has been converted from iron to aluminum, and weight has been significantly reduced.
• the demand for thinner batteries, such as 4 mm and 3 mm is increasing, and the use of film batteries that use aluminum laminate film as an exterior material is accelerating.
• film-type lithium-ion secondary batteries are increasingly being used in various fields as high-capacity, space-saving power sources.
• lithium disposed in a cell is brought into electrochemical contact with a negative electrode.
• lithium is supported by electrochemical contact between lithium and the negative electrode by using a material having holes that penetrate the front and back surfaces, such as expanded metal, for example, as the positive electrode current collector and the negative electrode current collector. It can proceed smoothly. Further, by arranging lithium so as to face the negative electrode or the positive electrode, lithium can be smoothly supported.
• the unevenness of the loading between the negative electrode placed near lithium and the negative electrode placed away from lithium, and the center and the end of a single negative electrode. May occur.
• there is no method for confirming whether a predetermined amount of lithium is carried and the only method is to refer to the voltage of the power storage device.
• the electrolyte is injected. At this point, the loading of lithium is started. However, when the electrolyte is injected, the electrodes are not yet firmly fixed, so that there is a problem that the negative electrode becomes rigid in a wavy state.
• the temperature of the electrolyte rises because the negative electrode generates heat, but if the temperature of the electrolyte rises while the cell is not completely sealed, the solvent evaporates, etc. Failure will occur.
• the composition of the solvent may change and the characteristics may vary between cells.
• an object of the present invention is to be able to easily manufacture and confirm whether or not a predetermined lithium is carried, and to be able to control the potential of the positive electrode or the negative electrode during charge and discharge, and to further reduce the lithium ion It is an object of the present invention to provide a power storage device capable of easily preventing unevenness in carrying and deformation of a negative electrode, and a method for manufacturing the same. Disclosure of the invention
• a power storage device in claim 1 includes a positive electrode, a negative electrode, a lithium electrode, and an electrolyte capable of transferring lithium ions,
• the lithium electrode is arranged so as not to directly contact the negative electrode and the z or the positive electrode.
• the lithium electrode By passing a current between the lithium electrode and the negative electrode and the Z or the positive electrode through an external circuit, the lithium electrode is It is characterized in that lithium can be supplied to Z or the positive electrode.
• unevenness of lithium loading on the negative electrode and / or the positive electrode deformation of the cell, temperature rise of the electrolytic solution in a state where the cell is not completely sealed, etc.
• the problem can be solved easily.
• the lithium disposed in the cell and the negative electrode were brought into electrochemical contact with each other, so that the lithium began to be supported when the electrolyte was injected.
• problems such as uneven loading between the portion where lithium was easily loaded and the portion where lithium was not easily loaded, and the fact that the anode was stiffened in a wavy state.
• the point of lithium loading can be easily controlled.
• the positive electrode, Lithium can be supported on the negative electrode while maintaining the flatness of the negative electrode, and a power storage device with high surface flatness can be easily manufactured.
• the lithium storage was started in a state where the power storage device was not completely sealed, and the temperature of the electrolytic solution was increased, and the solvent was evaporated. Since the point of time when lithium is supported can be easily controlled, it is possible to easily avoid an increase in the temperature of the electrolytic solution when the power storage device is not completely sealed.
• the potential difference between the lithium and the negative electrode was 0 V because the lithium and the negative electrode arranged in the cell were brought into electrochemical contact with each other.
• the potential of the negative electrode was higher than 0 V, so it took time to carry lithium.
• the current was passed through an external circuit between the negative electrode and the lithium electrode. For example, a negative voltage can be applied between the negative electrode and lithium to forcibly carry lithium, and the time required for carrying lithium can be reduced.
• mossy metallic lithium was generated on a part of the negative electrode and caused a short-circuit, but in the present invention, it is possible to control the current flowing through an external circuit between the negative electrode and the lithium electrode. Therefore, it is also possible to carry the metal at a current that does not generate mossy metallic lithium.
• the power storage device of the present invention does not require a complicated manufacturing process such as a method in which a cell having metal lithium as a counter electrode is assembled separately from the power storage device and a predetermined amount of lithium is supported on the negative electrode, and thus the power storage device can be easily manufactured.
• the lithium electrode only needs to be able to supply lithium to the negative electrode and z or the positive electrode.
• lithium is supported on the negative electrode by bringing lithium disposed in the cell and the negative electrode into electrochemical contact with each other, as described above.
• a lithium electrode can also be used as a reference electrode.
• the loading of lithium is started before sealing, which has the above-mentioned problem.However, to check whether a predetermined amount of lithium is loaded on the negative electrode, the potential difference between the lithium electrode and the negative electrode is measured. By doing so, it is possible to grasp appropriately. In this case, providing both a lithium electrode for supplying lithium to the negative electrode and a lithium electrode as a reference electrode at the same time can prevent uneven lithium loading, suppress cell deformation and determine the amount of lithium carried. Is more preferable.
• the power storage device according to the invention described in claim 2 is characterized in that a lithium salt aprotic organic solvent solution is used as the electrolyte.
• the power storage device according to the invention according to claim 3, wherein the positive electrode and the negative electrode are formed on a positive electrode current collector and a negative electrode current collector, respectively. Each is characterized by having holes penetrating the front and back surfaces.
• the lithium ion can freely move between the electrodes through the through hole, the lithium is carried from the lithium electrode to the negative electrode and / or the positive electrode, and the charge / discharge is performed. Progresses smoothly.
• the lithium electrode is formed on a lithium electrode current collector made of a conductive porous body, and at least a part of the lithium electrode is It is embedded in the pores of the lithium electrode current collector.
• the lithium is supported on the negative electrode and / or the positive electrode from the lithium electrode, and Disappearance of the electrode is preferable because the gap generated between the electrodes due to the disappearance of the lithium electrode is reduced.
• the power storage device according to the invention set forth in claim 5 is characterized in that the power storage device includes an outer container made of a laminate film.
• the use of a laminate film as the outer container is preferable because the power storage device can be reduced in size and weight. Also, in the case of a film type power storage device protected by a laminate film, the contact pressure from the outer container is weak, and in particular, electrode distortion, wrinkles, etc., tend to appear as cell distortion as they are.
• the power storage device according to the invention described in claim 6 is characterized in that the lithium electrode is disposed so as to face the negative electrode and / or the positive electrode.
• lithium by arranging the lithium electrode so as to face the negative electrode and Z or the positive electrode, lithium can be smoothly carried from the lithium electrode to the negative electrode and Z or the positive electrode, preferable.
• a power storage device is characterized by including an electrode stack unit in which three or more electrode pairs each including a positive electrode and a negative electrode are stacked. According to the invention set forth in claim 7, by stacking three or more electrode pairs each including a positive electrode and a negative electrode, the surface area of the electrodes can be increased without increasing the area of the power storage device, so that a compact This is preferable because the internal resistance is small and the storage capacity is large.
• a power storage device is characterized by comprising an electrode stacking unit in which an electrode pair including a positive electrode and a negative electrode is wound.
• the surface area of the electrode can be increased without increasing the area of the power storage device. This is preferable because the internal resistance is small and the storage capacity is large.
• the power storage device according to the invention described in claim 9 is a capacitor.
• the positive electrode contains a material capable of reversibly supporting lithium ions and anions as a positive electrode active material
• the negative electrode has a negative electrode active material.
• the negative electrode active material having a larger capacitance per unit weight than the capacitance per unit weight of the positive electrode active material is used; By making the material weight heavier than the anode active material weight, the capacitance and capacitance of the capacitor can be increased.
• the negative electrode contains a material capable of reversibly supporting lithium ion as a negative electrode active material, a predetermined amount of lithium is pre-loaded on the negative electrode in order to obtain a necessary capacity as the negative electrode capacity, thereby reducing the negative electrode potential. Energy can be reduced, the withstand voltage of the capacitor can be increased, and the energy density can be improved.
• by lowering the negative electrode potential it is possible to further increase the amount of change in the potential in discharging the positive electrode.
• the power storage device wherein the negative electrode active material is a heat-treated product of an aromatic condensation polymer, and the atomic ratio of hydrogen atoms to Z carbon atoms is 0.50. It is an insoluble and infusible substrate having a polyacene skeleton structure of about 0.05.
• the insoluble and infusible substrate having a polyacene-based skeleton structure used as the negative electrode active material has a property such as swelling and shrinking with respect to insertion and desorption of lithium ions.
• Excellent in cycle characteristics because there is no structural change, and because it has an isotropic molecular structure (higher-order structure) for lithium ion insertion and desorption, it has excellent characteristics for rapid charging and discharging. A device is obtained and preferred.
• the power storage device according to the invention described in claim 12 is characterized in that part of lithium still exists in the lithium electrode after the completion of the lithium supply step.
• the same lithium electrode can be used as the reference electrode, and the configuration of the power storage device is simplified. Is preferable. Then, this existing lithium can be used for regeneration of the capacity of the power storage device.
• the electric device according to the invention described in claim 13 is an electric device equipped with the power storage device according to claims 1 to 12, and includes electric appliances including general household electric appliances. It is also used for vehicles such as cars and bicycles, and equipment for storing natural energy.
• the method for manufacturing a power storage device according to the invention described in claim 14 includes the three electrodes of a positive electrode, a negative electrode, a lithium electrode, and an electrolyte capable of transporting lithium ions, which are arranged so as not to directly contact each other.
• a power storage device assembling step of sealing with an outer container, and passing a current between the lithium electrode and the negative electrode and the Z or the positive electrode through the external circuit to thereby transfer lithium from the lithium electrode to the negative electrode and the negative electrode or the positive electrode. And supplying lithium.
• the lithium electrode and the negative electrode and the Z or positive electrode are connected through an external circuit.
• the entire amount of lithium present in the lithium electrode is consumed as lithium ions, so that a highly safe power storage device can be obtained.
• the supply of lithium may be made by short-circuiting the lithium electrode to the negative electrode and the negative electrode or the positive electrode, the lithium supply step is simple.
• the method for manufacturing a power storage device according to the invention according to claim 16 is characterized in that: It is characterized in that some lithium is present in the lithium electrode after the lithium supply step.
• a predetermined amount of lithium can be supplied smoothly.
• the resistance of the lithium electrode increases because the area of the lithium metal or the like gradually decreases, and it takes time to consume the entire amount.
• a predetermined amount of lithium is consumed. Even if consumed, the area of lithium metal does not change, making it possible to supply lithium metal smoothly.
• the method for using a power storage device according to the invention according to claim 17 uses the present lithium electrode as a reference electrode, measures a positive electrode potential and a negative electrode potential, and uses a positive electrode or a negative electrode during charge / discharge of the power storage device. It is characterized in that the potential of the negative electrode can be controlled.
• the charge / discharge control of the power storage device can be controlled not by the voltage control between the positive electrode and the negative electrode but by the potential difference between the negative electrode and the reference electrode, that is, the negative electrode potential. For example, it is possible to terminate charging before the negative potential falls below 0 V when charging the power storage device.
• the method for using a power storage device according to the invention according to claim 18 is characterized in that after the use of the power storage device or after the characteristic deterioration, the lithium electrode is connected to the negative electrode and the Z or positive electrode through the external circuit. It is characterized in that lithium is supplied from the lithium electrode to the negative electrode and / or the positive electrode by passing a current therebetween.
• the power storage device of the present invention is characterized by having three electrodes: a positive electrode, a negative electrode, and a lithium electrode.
• lithium is carried on the negative electrode and the Z or the positive electrode by passing a current between the negative electrode and the Z or the positive electrode and the lithium electrode using an external circuit. Therefore, problems such as uneven loading of lithium on the negative electrode and / or the positive electrode, deformation of the cell, and an increase in the temperature of the electrolyte solution when the cell is not completely sealed can be easily solved.
• “Positive electrode” refers to the side on which current flows out during discharging and current flows in during charging.
• Negative electrode refers to the side where current flows in during discharging and current flows out during charging.
• lithium ions carried on the negative electrode escape, move in the electrolyte, and are carried on the positive electrode.
• the lithium ions carried on the negative electrode are again carried on the negative electrode.
• FIG. 1 is a perspective view showing the internal structure of a power storage device of the present invention.
• the internal structure of the power storage device is indicated by a solid line
• the outer container of the power storage device is indicated by a broken line.
• a three-electrode laminated unit in which the positive electrode 1, the negative electrode 2, the lithium electrode 7, and the separator 3 are laminated is installed inside the laminating films 4 and 5, and an electrolyte capable of transporting lithium ions is injected. After the liquid is applied, the two laminated films 4 and 5 are sealed by heat fusion or the like.
• the positive electrode 1 on which the positive electrode mixture 1c containing the positive electrode active material, etc. is formed, and on the negative electrode current collector 2a, the negative electrode active material, etc. are contained.
• the negative electrode 2 formed with the negative electrode mixture 2 c is laminated via the separator 3 so as not to be in direct contact with each other to form an electrode laminated unit 6.
• the negative electrode 2 and the lithium electrode 7 have a structure in which they do not come into contact in the cell. If the negative electrode 2 and the lithium electrode 7 are brought into contact, the loading of lithium will start when the electrolyte is injected, and even if the lithium is loaded on the negative electrode, the temperature of the electrolytic solution will be reduced even if the cell is not completely sealed. Problems like rising Therefore, it is not preferable.
• FIG. 2 is a bottom view of the power storage device of FIG. 1
• FIG. 3 is a cross-sectional view taken along the line I-I 'of FIG.
• the electrode laminated unit 6 has four layers of the positive electrode 1 and the negative electrode 2, respectively.
• the structure of the electrode laminated unit is not particularly limited, and the electrode laminated unit 6 has at least one layer of the positive electrode and the negative electrode.
• the number of layers of the negative electrode is not particularly limited.
• the lithium electrode 7 is arranged above the electrode laminated unit 6, but the position, the number of layers, and the shape of the lithium electrode are not limited thereto. However, in order to carry lithium smoothly, it is preferable to arrange the lithium electrode so as to face the negative electrode or the positive electrode.
• the power storage device of the present invention has a structure in which the negative electrode and the lithium electrode are not brought into contact in the cell.
• a separator 3 is provided between each of the positive electrode 1, the negative electrode 2, and the lithium electrode 7 so that they do not directly contact each other.
• the inside of the cell is filled with a liquid electrolyte capable of transporting lithium ions, and the electrolyte is also impregnated in the separator 3 separating each electrode.
• the electrolyte is usually in a liquid state and is impregnated into the separator 3.However, when the separator 3 is not used, the positive electrode 1, the negative electrode 2, and the lithium electrode 7 do not come into direct contact with each other. In order to prevent this, the electrolyte may be used in a gel or solid state.
• Each of the positive electrode current collector la, the negative electrode current collector 2a, and the lithium electrode current collector 7a has a hole (not shown) penetrating the front and back surfaces, and lithium ions can freely pass through the through hole. Can move between poles. Therefore, the loading of lithium from the lithium electrode to the negative electrode proceeds smoothly. In addition, the movement of lithium ions between the positive electrode and the negative electrode during charge / discharge proceeds smoothly.
• each of the positive electrode current collector la, the negative electrode current collector 2a, and the lithium electrode current collector 7a has a lead portion serving as a terminal connection portion A ′, B ′, C. .
• the terminal weld B '(1 piece) of a and the lithium pole terminal 7b are welded respectively.
• Laminating films 4 and 5 are sealed with positive terminal 1b, negative terminal 2b, lithium
• the positive electrode terminal 1b, the negative electrode terminal 2b, and the lithium electrode terminal 7b are attached to the laminated films 4 and 5, respectively, with the heat-sealed portions A and B shown in FIG. Heat-sealed at B and C. That is, in the example of FIG. 2, the power storage devices are provided at the heat-sealed portions A, B, and C between the laminated films 4 and 5 and the respective terminals, and at the heat-sealed portions D between the laminated films 4 and 5. And sealed. Therefore, the positive electrode terminal 1b, the negative electrode terminal 2b, and the lithium electrode terminal 7b extend out of the battery between the laminating films 4 and 5, and the positive electrode 1, the negative electrode 2, and the lithium electrode 7 It can be connected to an external circuit through.
• the shape and size of the positive electrode terminal lb, the negative electrode terminal 2b, and the lithium electrode terminal 7b are not particularly limited, but it is preferable to be as thick and wide as possible as long as sufficient airtightness can be obtained within a limited cell volume. This is preferable because the resistance of the terminal is reduced. It is preferable that the shape and size of each terminal be appropriately selected according to the characteristics of the target cell.
• each of the current collectors la, 2a, and 7a has a hole that penetrates the front and back surfaces, and lithium ions can freely move between the electrodes through the through hole.
• lithium ions eluted from the lithium metal 7c into the electrolyte are converted into the respective current collectors 7a. , 2a, and 1a, and are carried by the negative electrode mixture 2c.
• lithium ions carried on the negative electrode mixture 2c escape and move in the electrolyte to be carried on the positive electrode mixture 1c.
• lithium metal 7c When a voltage of 0 V is applied to the negative electrode 2 with respect to the lithium electrode 7, the lithium metal 7c releases lithium ions and decreases.
• the amount of lithium metal 7c (lithium contained in the lithium electrode) to be placed in the power storage device should be large enough to obtain the desired negative electrode capacitance, but more than that In this case, a predetermined amount of lithium metal 7c may be supported, and then lithium metal 7c may partially exist in the power storage device (the definition of the capacitance will be described later).
• Lithium metal 7 When c is partially present, it is possible to use the lithium electrode 7 as a reference electrode to confirm the potential of the positive electrode and the negative electrode. However, in consideration of safety, it is preferable to arrange only the necessary amount and carry the entire amount on the negative electrode, but it is desirable to appropriately set the lithium amount according to the purpose.
• the negative electrode includes a negative electrode mixture and a negative electrode current collector, and the negative electrode mixture contains a negative electrode active material capable of reversibly supporting lithium.
• the negative electrode active material is not particularly limited as long as it can support lithium reversibly, and examples thereof include graphite, various carbon materials, polyacene-based materials, tin oxide, and silicon oxide.
• An active material having a so-called amorphous structure such as a polyacene organic semiconductor (PAS), whose potential gradually decreases with the insertion of lithium and increases with desorption of lithium, is used for the negative electrode.
• PAS polyacene organic semiconductor
• the capacity is slightly increased. Therefore, it is desirable to appropriately set the amount of lithium within the range of the lithium storage capacity of the active material according to the required working voltage of the capacity.
• PAS has an amorphous structure, there is no structural change such as swelling or shrinking in response to lithium ion insertion and desorption, so it has excellent cycle characteristics, and isotropic molecules for lithium ion insertion and desorption. Since it has a structure (higher-order structure), it has excellent characteristics for rapid charging and rapid discharging, and is therefore suitable as a negative electrode active material.
• a heat-treated aromatic condensation polymer is used as the negative electrode active material.
• an insoluble infusible substrate having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms and Z carbon atoms is 0.50 to 0.05.
• the aromatic condensation polymer means a condensate of an aromatic hydrocarbon compound and an aldehyde.
• aromatic hydrocarbon compound so-called phenols such as phenol, cresol, xylenol and the like can be suitably used.
• Methylene bisphenols represented by the following formulas, or hydroxy-biphenyls and hydroxynaphthylenes. Of these, phenols, particularly phenol, are practically preferred.
• aromatic condensation polymer a part of the aromatic hydrocarbon compound having a phenolic hydroxyl group may be replaced with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene, toluene, and aniline.
• a substituted modified aromatic condensation polymer for example, a condensation product of phenol, xylene and formaldehyde can also be used.
• a modified aromatic polymer substituted with melamine or urea can be used, and a furan resin is also preferable.
• aldehydes such as formaldehyde, acetoaldehyde, and furfural can be used, and among these, formaldehyde is preferable.
• the phenol formaldehyde condensate may be any of a nopolak type, a resol type, or a mixture thereof.
• the insoluble infusible substrate is obtained by heat-treating the aromatic polymer, and any of the insoluble infusible substrates having the polyacene skeleton structure described above can be used.
• the insoluble infusible substrate used in the present invention can be produced, for example, as follows. That is, the above aromatic condensation polymer is gradually heated to an appropriate temperature of 400 to 800 ° C. in a non-oxidizing atmosphere (including vacuum) to obtain an atomic ratio of hydrogen atoms to Z carbon atoms (hereinafter H). / C) is from 0.5 to 0.05, preferably from 0.35 to 0.10.
• an insoluble infusible substrate having a specific surface area of 600 m 2 Zg or more by the BET method can be obtained by the above method.
• a solution containing an initial condensate of an aromatic condensation polymer and an inorganic salt, for example, zinc chloride is prepared, and the solution is heated and cured in a mold to obtain an insoluble infusible substrate having a high specific surface area. You can also.
• the cured product thus obtained is gradually heated in a non-oxidizing atmosphere (including vacuum) to a temperature of 350 to 800 ° C, preferably to an appropriate temperature of 400 to 750 ° C, By washing sufficiently with water or diluted hydrochloric acid, an insoluble infusible substrate having the above HZC and having a specific surface area of, for example, 600 m 2 Zg or more by a BET method can be obtained.
• a non-oxidizing atmosphere including vacuum
• the insoluble and infusible substrate used in the present invention has an X-ray diffraction (according to CuKo, the position of the main peak is present at 24 ° or less expressed by 2 °, and in addition to the main peak, 41 to 46 °).
• the insoluble infusible substrate has a polyacene skeleton structure in which an aromatic polycyclic structure is appropriately developed, and has an amorphous structure. It is suggested that lithium can be stably doped, so that it is useful as an active material for batteries.
• the negative electrode according to the present invention preferably contains the negative electrode active material such as PAS described above, and is formed by molding a negative electrode active material having a shape such as powder, granules, and short fibers that is easy to mold with a binder.
• a binder for example, a rubber binder such as SBR, a fluorine-containing resin such as polytetrafluoroethylene or polyvinylidene fluoride, or a thermoplastic resin such as polypropylene or polyethylene can be used. It is also preferable to use a fluorine binder.
• F / C fluorine-based binder having an atomic ratio of fluorine atoms and Z carbon atoms
• fluorine-based binder examples include polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, propylene-tetrafluoroethylene copolymer, and the like. Further, a fluorine-containing polymer in which hydrogen in the main chain is substituted with an alkyl group can also be used.
• F / C is 1, and in the case of the vinylidene fluoride-3 fluoroethylene copolymer, when the molar fraction of the vinylidene fluoride is 50% and when it is 80%, FZC is Is 1.25, 1.1. Further, in the case of a propylene tetrafluoroethylene copolymer, when the propylene mole fraction is 50%, FZC is 0.75.
• polyvinylidene fluoride and a vinylidene fluoride-tetrafluoroethylene copolymer having a molar fraction of 50% or more of vinylidene fluoride are preferred, and practically, polyvinylidene fluoride is preferably used.
• a conductive material such as acetylene black, graphite or metal powder may be appropriately added to the negative electrode active material as needed.
• the positive electrode includes a positive electrode mixture and a positive electrode current collector, and the positive electrode mixture contains a positive electrode active material.
• the positive electrode active material is not particularly limited as long as it can reversibly carry lithium ions and Z or an anion such as tetrafluoroporate. Examples thereof include activated carbon, a conductive polymer, and a polyacene-based material. Can be mentioned. Among these, an insoluble infusible substrate having a polyacene skeleton structure, which is a heat-treated aromatic condensation polymer and has an atomic ratio of hydrogen atoms to carbon atoms of 0.5 to 0.05. (Hereinafter referred to as PAS) is preferable because high capacity can be obtained.
• the positive electrode in the present invention is formed by adding a conductive material, a binder, and the like to the positive electrode active material as needed, and the type and composition of the conductive material and the binder can be appropriately set.
• the conductive material for example, a carbon-based material such as activated carbon, power pump rack, acetylene black, and graphite can be suitably used.
• the mixing ratio of the conductive material varies depending on the electric conductivity of the active material, the electrode shape, and the like, but it is appropriate to add the conductive material at a ratio of 2 to 40% with respect to the active material.
• the binder may be any one that is insoluble in the electrolyte solution described below.
• a rubber-based binder such as SBR
• a fluorinated resin such as polytetrafluoroethylene or polyvinylidene fluoride, polypropylene, or polyethylene And the like can be preferably used.
• the mixing ratio is preferably 20% or less based on the active material.
• the positive electrode current collector and the negative electrode current collector in the present invention are not particularly limited, but those each having a hole penetrating the front and back surfaces are preferable. For example, expanded metal, punched metal, mesh, foam, and the like And the like.
• the form, number, and the like of the through holes are not particularly limited, and can be appropriately set so that lithium ions in the electrolyte described below can move between the front and back of the electrode without being interrupted by the electrode current collector. .
• the potential of the negative electrode and the potential of the Z or positive electrode can be measured using the lithium electrode, and the potential of the positive electrode or the negative electrode can be controlled during charging and discharging of the power storage device.
• the positive electrode current collector and the negative electrode current collector are more likely to have a larger surface area than the case where a non-porous foil is used for the current collector. It is preferable to provide a hole penetrating the back surface.
• the porosity of the electrode current collector is defined as the ratio obtained by converting the ratio of ⁇ 1-(current collector weight Z current collector specific gravity) / (current collector apparent volume) ⁇ into a percentage.
• the porosity is high, it is desirable that lithium is carried on the negative electrode for a short time and unevenness is not easily generated. However, it is difficult to hold the active material in the opening, and the strength of the electrode is weak, so that the electrode is formed. Yield decreases. In addition, the active material at the openings, especially at the edges, is removed. It is easy for the battery to fall, causing a short circuit inside the battery.
• the porosity and pore size of the current collector be appropriately selected in consideration of the battery structure (laminated type, wound type, etc.) and productivity.
• the material of the electrode current collector various materials generally proposed for organic electrolyte batteries can be used.
• the positive electrode current collector aluminum, stainless steel, etc.
• stainless steel, copper, Nickel or the like can be used respectively.
• the lithium electrode includes a lithium metal and a lithium electrode current collector.
• the lithium metal of the present invention includes, besides lithium metal, a substance containing at least lithium and capable of supplying lithium ion, such as a lithium aluminum alloy.
• the thickness of the lithium metal is 50 to 300 m, preferably 80 to 200 m, and more preferably 100 to 160 m.
• the lithium electrode has a structure in which lithium metal is attached on a lithium electrode current collector made of a conductive porous material.
• a conductive porous body such as a stainless mesh as the lithium electrode current collector.
• the lithium metal is embedded in the pores of the lithium electrode current collector.
• 80% or more of lithium metal is filled and arranged in the pores of the conductive porous body.
• the amount of lithium carried on the negative electrode can be determined each time depending on the negative electrode material used and the characteristics required for the power storage device.
• the lithium electrode current collector on which the lithium electrode is formed is arranged so as to face the negative electrode and Z or the positive electrode.
• lithium can be smoothly carried on the negative electrode and / or the positive electrode.
• the negative electrode and the lithium electrode supported on the z or the positive electrode by arranging the negative electrode and the lithium electrode supported on the z or the positive electrode locally at a specific position, it is possible to improve the degree of freedom in cell design and the mass productivity, Charge and discharge characteristics can be provided.
• an electrolyte used for the power storage device of the present invention an electrolyte that can transfer lithium ions is used.
• Such an electrolyte is usually in a liquid state and is impregnated into the separator.
• the positive electrode, the negative electrode, and the lithium electrode do not come into direct contact with each other.
• the electrolyte may be used in a gel or solid state.
• the separator it is possible to use, for example, a porous material having continuous air holes that are durable with respect to the electrolyte solution or the electrode active material and has no electron conductivity.
• an aprotic organic solvent of a lithium salt As an electrolyte capable of transporting lithium ions, it is preferable to use an aprotic organic solvent of a lithium salt from the viewpoint that lithium ions are stably present without causing electrolysis even at a high voltage.
• the aprotic organic solvent includes, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, getyl carbonate, arbutyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane and the like. Furthermore, a mixed solution obtained by mixing two or more of these aprotic organic solvents can also be used.
• the supporting electrolyte comprising a lithium ion source, for example L i I, L i C 1 0 4, L i A s F 6, L i BF 4, L i PF 6 , and the like.
• the above supporting electrolyte and solvent are mixed in a sufficiently dehydrated state to form an electrolyte.
• concentration of the supporting electrolyte in the electrolyte is at least 0.1 mol / m to reduce the internal resistance due to the electrolyte. It is preferably at least I, more preferably in the range of 0.5 to 1.5 mol 1.
• the material of the outer container of the power storage device of the present invention is not particularly limited, and various materials generally used for batteries can be used, and metal materials such as iron and aluminum, and film materials can be used.
• the shape of the outer container is not particularly limited, and can be appropriately selected depending on the intended use, such as a cylindrical shape or a square shape. From the viewpoint of reducing the size and weight of the power storage device, it is preferable to use a film-type outer container using an aluminum laminated film.
• a general film battery uses a three-layer laminate film having a nylon film on the outside, an aluminum foil in the center, and an adhesive layer of modified polypropylene or the like on the inside as the exterior material.
• the laminated film is deep drawn according to the size and thickness of the electrodes and the like to be placed inside.
• a unit in which a positive electrode, a negative electrode and a separator are laminated or wound is installed, and the electrolyte is supplied. After the injection, the laminated film is sealed by heat fusion or the like.
• the positive electrode terminal mainly aluminum foil with a thickness of 100
• the negative electrode terminal mainly nickel foil with a thickness of 100m
• the sealing of the laminated film is performed by a simple method in which the positive electrode terminal and the negative electrode terminal are sandwiched and fused.
• the contact pressure from the outer container of a film battery is weaker than that of a battery using a metal case such as a cylindrical or square battery, so that the electrode distortion and wrinkles appear as the cell distortion as it is.
• the negative electrode becomes rigid when lithium is carried. However, when lithium is carried while the electrode is wavy, it becomes rigid while waving, so that the cell is distorted and the performance is reduced. However, if lithium is carried on the negative electrode while maintaining the flatness of the positive and negative electrodes by virtue, etc., the negative electrode becomes rigid while maintaining the flatness, eliminating distortion of the cell itself and performance. Can be improved.
• the laminated films 4 and 5 are used as the outer container, and the laminating film 5 is deep-drawn by the thickness of the three-electrode laminated unit 8, but either one of the laminated films 4 and 5 or Both can be deep drawn.
• a set of two laminated films is used as a laminate film, they are overlapped so as to cover the contents, and the stacked outer portion is heat-sealed to seal the contents.
• the film member is not limited to the sheet-like film used in FIG. 1, but may be a film member which has been formed into a tubular or bag-like shape in advance.
• the contents are sealed by heat sealing two opposing sides, and in the case of using a bag-shaped film member, one open side is heated. By sealing, the contents are sealed.
• the power storage device of the present invention refers to a device that can be charged and discharged, and specifically refers to a secondary battery, a capacitor, and the like. Regardless of the use of the power storage device of the present invention in any application, the basic configuration is the same in that the power storage device includes a positive electrode, a negative electrode, a lithium electrode, and an electrolyte capable of transferring lithium ions. is there.
• the same active material mainly activated carbon
• the active material used for the positive and negative electrodes has a potential of about 3 V when the cell is assembled.
• the anion forms an electric double layer on the surface of the positive electrode, and the positive electrode potential rises.
• the cations form an electric double layer on the surface and the potential drops.
• anions are released from the positive electrode and cations are released from the negative electrode into the electrolyte, causing the potential to drop and rise, respectively, and return to around 3 V.
• the shapes of the charge and discharge curves of the positive and negative electrodes are almost line-symmetric around 3 V, and the potential change of the positive electrode and the potential change of the negative electrode are almost the same.
• the positive electrode has almost only anion and the negative electrode has almost only cation.
• the power storage device of the present invention when used as a capacitor, it is preferable to use an active material capable of reversibly supporting lithium ion and Z or anion for the positive electrode.
• an active material capable of reversibly supporting lithium ion and Z or anion for the positive electrode.
• the capacitance and the capacitance are defined as follows.
• the capacitance of the cell indicates the slope of the cell's discharge force, and the unit is F (farads).
• the capacitance per unit weight of the cell is the positive electrode activity that fills the cell's capacitance in the cell.
• the value is divided by the total weight of the material weight and the negative electrode active material weight, the unit is FZ g, the positive electrode capacitance is the slope of the positive electrode discharge curve, the unit is F, and the positive electrode capacitance per unit weight is The capacity is a value obtained by dividing the capacitance of the positive electrode by the weight of the positive electrode active material filled in the cell, and the unit is FZ g.
• the capacitance of the negative electrode indicates the slope of the discharge curve of the negative electrode. Is F, and the capacitance per unit weight of the negative electrode is the value obtained by dividing the capacitance of the negative electrode by the weight of the negative electrode active material filled in the cell, and the unit is FZ g.
• the cell capacity is the difference between the discharge start voltage and the discharge end voltage of the cell, that is, the product of the amount of voltage change and the cell capacitance.
• the unit is C (coulomb), and 1 (3 is 1 A per second).
• the positive electrode capacity is the positive electrode potential at the start of discharge and the positive electrode potential at the end of discharge.
• the difference between the negative electrode potential (amount of change in the positive electrode potential) and the positive electrode capacitance is expressed in C or mAh.
• the negative electrode capacity is the difference between the negative electrode potential at the start of discharge and the negative electrode potential at the end of discharge (negative electrode potential). Change) and the capacitance of the negative electrode.
• the unit is C or mAh.
• PASS As a material having an electrostatic capacity three times or more the electrostatic capacity per unit weight of the positive electrode active material, for example, PASS is given.
• the present inventors have found that a capacitance of over 65 FZ g is obtained when PAS is loaded (charged) with 40 O mA h / g of lithium and then discharged, and a capacitance of 50 O mA h / g is obtained. It has been found that when charging more than g of lithium, a capacitance of more than 75 FZ g can be obtained.
• the capacitance per unit weight of the positive and negative electrodes of a general electric double layer capacity is about 60 to 200 FZg, it can be seen that PAS has a very large capacitance.
• a capacitance of at least three times the capacitance per unit weight of the positive electrode is ensured, and the weight of the positive electrode active material is reduced.
• a combination that is heavier than the negative electrode active material weight is most preferable because the effect is obtained.
• the capacitance per unit weight of the negative electrode active material is less than three times the capacitance per unit weight of the positive electrode active material, the same amount of the same active material is used for the positive electrode and the negative electrode.
• the increase in capacitance is smaller than that of a conventional electric double layer capacitor.
• the capacitance per unit weight of the negative electrode active material is more than three times the capacitance per unit weight of the positive electrode active material, if the weight of the positive electrode active material is smaller than the weight of the negative electrode active material, the conventional It is not preferable that the increase in capacitance is smaller than that of the electric double layer capacitor.
• the capacitor according to claim 10 of the present invention achieves high capacity by the following three effects.
• the first effect is that the use of a negative electrode active material having a larger capacitance per unit weight than the capacitance per unit weight of the positive electrode active material allows the negative electrode to remain unchanged without changing the potential change amount of the negative electrode. Since it is possible to reduce the weight of the active material, the filling amount of the positive electrode active material increases, and the capacitance and capacity of the cell increase.
• Another design In other words, since the capacitance of the negative electrode active material is large, the amount of change in the potential of the negative electrode is small, and as a result, the amount of change in the potential of the positive electrode is large, and the capacitance and capacity of the cell are large.
• the second effect is that a predetermined amount of lithium is preliminarily supported on the negative electrode in order to obtain the required capacity as the negative electrode capacity, and the positive electrode potential at the time when lithium is preliminarily supported on the negative electrode is about 3 V. In contrast, the negative electrode potential is lower than 3 V.
• the voltage when the cell voltage is increased until the electrolyte is oxidatively decomposed is substantially determined by the positive electrode potential.
• the withstand voltage of the capacitor of the present invention having lithium in advance is higher than that of the capacitor having a normal cell configuration, because the negative electrode potential is lower.
• the configuration of the present invention can be set as high as 3 V or more, and the energy density is improved.
• a third effect is an increase in the capacity of the positive electrode due to a low negative electrode potential.
• the negative electrode potential is low, it is possible to further increase the amount of change in the potential in the discharge of the positive electrode.
• the positive electrode potential falls below 3 V at the end of discharge, and it is possible to lower the discharge potential to, for example, 2 V. (This is mainly due to the release of anions up to 3 V discharge and below 3 V. Doping of lithium ions has occurred and the potential has dropped).
• the potential of the positive electrode drops only to about 3 V at the time of discharge, but at that point the negative electrode potential also becomes 3 V and the cell voltage becomes 0 V. That is, the configuration of the present invention in which the positive electrode potential can be reduced to 2 V has a higher capacity than the conventional configuration of the electric double layer capacity that can only be reduced to 3 V.
• FIG. 1 is a perspective view showing Embodiment 1 according to the present invention.
• FIG. 2 is a plan view showing the first embodiment according to the present invention.
• FIG. 3 is a sectional view taken along the line II ′ of FIG.
• FIG. 4 is a sectional view taken along the line II-II 'of FIG.
• FIG. 5 is a sectional view showing a first example of a layer configuration of the three-electrode laminated unit according to the present invention.
• FIG. 6 is a sectional view showing a second example of the layer configuration of the three-electrode laminated unit according to the present invention.
• FIG. 7 is a cross-sectional view showing a third example of the layer configuration of the three-electrode laminated unit according to the present invention.
• FIG. 8 is a plan view showing a second embodiment according to the present invention.
• FIG. 9 is a plan view showing a third embodiment according to the present invention.
• FIG. 10 is a sectional view taken along the line I-I 'of FIG.
• FIG. 11 is a cross-sectional view taken along the line II--II of FIG.
• FIG. 12 is a plan view showing a fourth embodiment according to the present invention.
• FIG. 13 is a cross-sectional view taken along the line II ′ of FIG.
• FIG. 14 is a cross-sectional view taken along the line II-II of FIG.
• FIG. 15 is an exploded perspective view showing an example of the electrode stacking unit according to the present invention.
• FIG. 16 is an exploded perspective view showing an example of the electrode stacking unit according to the present invention.
• 1 is a positive electrode
• 2 is a negative electrode
• la is a current collector (positive electrode)
• 2a is a current collector (negative electrode)
• 1b is a positive electrode terminal
• 2b is a negative electrode terminal
• 1c is a positive electrode active material and a binder.
• 2c is a negative electrode mixture composed of a negative electrode active material and a binder
• 3 is a separator
• 4 is a laminating film
• 5 is a laminated film (deep drawing)
• 6 is an electrode laminating unit
• 7 is lithium.
• Electrode 7a is a lithium electrode current collector, 7b is a lithium electrode terminal, 7c is a lithium metal or lithium alloy, 8 is a three-electrode laminated unit, 9a, 9b and 9c are conductors, and 10 is a conductor.
• Electrode winding unit A: heat-sealed part between positive electrode terminal and outer film
• B heat-sealed part between negative electrode terminal and outer film
• C heat-sealed part between lithium electrode terminal and outer film
• D heat-sealed part Heat-sealed part
• a ' is terminal weld of positive electrode current collector and positive terminal
• B ' is the weld between the terminal weld of the negative electrode current collector and the negative electrode terminal
• C' is the weld between the terminal weld of the lithium electrode current collector and the lithium electrode terminal
• FIG. 1 is a diagram showing Embodiment 1 of a power storage device of the present invention, in which a film-type capacitor in which external terminals of a positive electrode and a negative electrode are respectively taken out from opposite sides, and a positive electrode terminal and a lithium terminal are taken out from the same side.
• FIG. 2 is a plan view of the first embodiment
• FIG. 3 is a sectional view taken along the line I-I 'of FIG. 2
• FIG. 4 is a sectional view taken along the line II-II' of FIG.
• a three-electrode stacked unit 8 is formed by providing a lithium electrode 7 on an electrode stacked unit 6 in which an electrode pair including a positive electrode 1 and a negative electrode 2 are sequentially stacked.
• the electrode stacking unit 6 is configured by using three negative electrode current collectors 2a and two positive electrode current collectors 1a.
• the electrode stacking unit 6 has a first negative electrode current collector 2a having a negative electrode 2 provided on the upper surface and a positive electrode 1 provided on both surfaces in order from the lower layer while sandwiching the separator 3 so that the positive electrode and the negative electrode do not directly contact each other.
• the provided third negative electrode current collector 2a is sequentially laminated.
• a lithium electrode current collector 7 a having a lithium electrode 7 provided on the lower surface is disposed on the electrode laminated unit 6 via a separator 3, thereby forming a three-electrode laminated unit 8.
• a positive electrode current collector 1a, a negative electrode current collector 2a, and a lithium electrode current collector 7a have lead portions serving as terminal connection portions A ′, B ′, and C, and the terminal connection portions are provided.
• the parts A ', B', and C are welded to the positive terminal 1b, the negative terminal 2b, and the lithium terminal 7b.
• the shape of the lead portion serving as the terminal welding portion is not particularly limited. This welding should be done by ultrasonic welding etc. by bundling out the lead parts of several positive electrode current collectors (or negative electrode current collectors). Is simple and suitable.
• the positive electrode terminal 1b and the negative electrode terminal 2b respectively protrude from opposite sides, and the positive terminal 1b and the lithium terminal 7b protrude from the same side. There are no restrictions on the location of the installation.
• the electrode stack unit 6 has four electrode pairs each including a pair of a positive electrode and a negative electrode.
• the number of electrode pairs in the electrode stack unit 6 is not particularly limited. Two or more layers may be provided. Further, an electrode stack unit 6 having two or more electrode pairs may be formed by winding an electrode pair including a pair of a positive electrode and a negative electrode.
• the electrode laminated unit 6 has at least one layer of the positive electrode and the negative electrode, it is not always necessary to provide one pair of the positive electrode and the negative electrode.
• one layer of a common positive electrode can be provided for two or more layers of a negative electrode.
• the position of the lithium electrode 7 is not particularly limited, and the lithium electrode 7 is provided in the lowermost layer. It may be provided on both the uppermost layer and the lowermost layer, or may be provided on the intermediate layer of the electrode stacking unit.
• a three-electrode laminated unit 8 having another layer configuration shown in FIGS. 5 to 7 may be used instead of the three-electrode laminated unit 8 of the first embodiment.
• FIG. 5 shows another layer configuration of the three-electrode laminated unit 8.
• a lithium electrode 7 in which lithium metal is pressed onto a lithium electrode current collector 7a is disposed below an electrode stack unit 6 in which a positive electrode 1, a separator 3 and a negative electrode 2 are sequentially stacked, and a three-electrode stack is provided.
• Unit 8 is formed.
• FIG. 6 shows another layer configuration of the three-electrode laminated unit 8.
• a lithium electrode 7 in which lithium metal is pressure-bonded to a lithium electrode current collector 7a is arranged above and below an electrode stack unit 6 to form a three-electrode stack unit 8.
• a lithium electrode 7 is arranged in the middle of two electrode stack units 6 to form a three-electrode stack unit 8.
• the arrangement position of the lithium electrode 7 can be appropriately changed.
• Several positive electrodes 1, negative electrodes 2, and lithium electrodes 7 stacked in the three-electrode stacked unit 8 shown in FIGS. 5 to 7 are bundled into one, and the conductors 9 a, 9 b, 9 Connected to c.
• the conductors 9a, 9b, 9c are, for example, a positive electrode terminal 1b, a negative electrode terminal 2b, and a lithium electrode terminal 7b.
• lithium When lithium is carried from the lithium electrode to the negative electrode, for example, when a voltage of 1.05 V is applied between the negative electrode and the lithium electrode through the conducting wires 9b and 9c, current flows into the lithium electrode 7, The lithium ions eluted from the lithium electrode 7 are carried (doped) by the negative electrode 2. At the time of discharging, lithium ions are released from the negative electrode 2 and carried on the positive electrode 1. At this time, current can be taken out through the conductive wires 9a and 9b. In addition, during charging, for example, if a 3 V voltage is applied between the positive electrode 1 and the negative electrode 2 through the conductive wires 9a and 9b, that is, if a current flows into the positive electrode 1, the lithium ions carried on the positive electrode 1 will be recharged. It is carried on the negative electrode 2.
• FIG. 8 is a plan view of the second embodiment.
• Embodiment 2 is characterized in that three-pole external terminals are protruded from the same side, and has the same configuration as Embodiment 1 except for this point.
• the positive electrode terminal lb, the negative electrode terminal 2b, and the lithium electrode terminal 7b extend from the same side.
• the positive electrode terminal 1b, the negative electrode terminal 2b, and the lithium electrode terminal 7b are drawn from the opposite sides, and the three-pole terminal shown in FIG. 8 is drawn from the same side.
• the electrode size can be increased in the second embodiment by the width indicated by (*).
• FIG. 9 is a plan view showing the third embodiment. is there.
• Embodiment 3 is a plan view of a capacitor having a winding type structure in which a plate-like lithium electrode 7 is disposed at the center.
• FIG. 10 is a sectional view taken along the line I-I 'of FIG. 9, and
• FIG. 11 is a sectional view taken along the line II-II' of FIG. Since the common reference numerals in Embodiment 1 and Embodiment 3 indicate the same configuration, only different portions will be described here in detail.
• a plate-shaped lithium electrode 7 is arranged at the center of the winding type structure.
• the lithium electrode 7 is formed on both sides of the lithium electrode current collector 7a.
• the positive electrode 1 and the negative electrode 2 are formed on one surface of a lipon-shaped positive electrode current collector 1a and a negative electrode current collector 2a, respectively.
• a lithium electrode current collector 7a having lithium electrodes 7 formed on both sides as cores
• a separator 3, a negative electrode 2, a separator 3, and a positive electrode 1 are stacked in this order and rolled into an elliptical shape, followed by press molding. I have.
• FIG. 12 is a plan view showing the fourth embodiment.
• Embodiment 4 is a plan view of a capacity having a winding type structure in which a lithium electrode 7 is arranged on the outermost periphery.
• FIG. 13 is a sectional view taken along the line II ′ of FIG. 12, and
• FIG. 14 is a sectional view taken along the line II ′ of FIG. Since the common reference numerals in Embodiment 1 and Embodiment 4 indicate the same configuration, only different portions will be described in detail here.
• the lithium electrode 7 is arranged on the outermost periphery of the electrode stacking unit having the winding type structure.
• the positive electrode 1 and the negative electrode 2 are formed on one surface of a lipon-shaped positive electrode current collector 1a and a negative electrode current collector 2a, respectively. Further, the lithium electrode 7 has a lithium metal current collector 7a attached to one side of a lithium electrode current collector 7a. After forming a coiled-type electrode stacking unit by stacking and winding the separator 3, the cathode 1, the separator 3, and the anode 2 in this order, lithium metal 7c is applied to one side of the lithium electrode current collector 7a. The one-turned lithium electrode 7 with the lithium metal 7c side of the attached lithium electrode 7 inside is press-formed.
• the positive electrode is formed by mixing a positive electrode active material with a binder resin to form a slurry, coating on a positive electrode current collector, and drying.
• a negative electrode is formed by mixing a negative electrode active material with a binder resin to form a slurry, coating the slurry on a negative current collector, and drying.
• the lithium electrode is formed by pressing lithium metal on a lithium electrode current collector made of a conductive porous material. The thickness of each layer can be appropriately determined according to the application.
• the thickness of the positive electrode current collector and the negative electrode current collector is about 100 to 100, and the thickness of the electrode active material coating. Is about 50 to 300 / m per side. Therefore, the thickness of the (electrode active material + electrode current collector) after the electrodes are formed is about 100 to 500 m in total.
• the thickness of the lithium electrode current collector is about 10 to 200, and the thickness of the lithium metal serving as the lithium electrode is about 50 to 300 m.
• the electrode current collector on which the electrodes are formed is dried, it is cut into a width suitable for the size of the outer container of the power storage device.
• the terminal When creating an electrode stack unit with a wrap-around structure, cut it into a ripon shape.
• the terminal may be pressed into a shape having a lead portion as a terminal welding portion.
• FIGS. 15 and 16 are exploded views of the electrode stacking unit, showing the shape of the terminal welding portion and the stacking direction.
• Fig. 15 shows an example in which the positive electrode terminal weld and the negative electrode terminal weld protrude from opposite sides, respectively.
• Fig. 16 shows the positive electrode terminal weld and the negative electrode terminal weld in the same side This is an example that comes out of.
• the directions of the positive and negative terminals are not limited to these two types.
• the triode laminated unit which is welded to the external terminal, is installed inside the outer container, and the outer container is closed by heat welding, etc., leaving the electrolyte inlet. At this time, at least a part of the external terminal is exposed to the outside of the outer container so that it can be connected to an external circuit. After the electrolyte is injected from the electrolyte injection port of the outer container and the inside of the outer container is filled with the electrolyte, the electrolyte injection port is closed by heat fusion or the like, and the outer container is completely sealed.
• the power storage device of the invention is obtained.
• the thus obtained power storage device of the present invention can cause the negative electrode to carry lithium by, for example, passing a current between the lithium electrode and the negative electrode through the negative electrode terminal and the lithium electrode terminal.
• a voltage of 1.0 V between the negative electrode and the lithium electrode current is passed from the external circuit to the lithium electrode
• the lithium ions eluted from the lithium electrode move through the electrolyte and are carried on the negative electrode. Is done.
• the negative electrode becomes rigid while maintaining the flatness, so that the cell itself is not distorted and the cell performance is improved.
• the timing of preloading lithium on the negative electrode is not particularly limited. However, if the power storage device is charged before lithium is supported on the negative electrode, the positive electrode potential may increase and decomposition of the electrolyte may occur. It is preferable to short-circuit the negative electrode terminal and the lithium electrode terminal before charging.
• the lithium metal at the lithium electrode gradually decreases.However, when some lithium metal at the lithium electrode is still present after the lithium ions are supported at the negative electrode, the lithium metal It is also possible to use the remaining lithium electrode as a reference electrode to confirm the potential of the positive electrode and the negative electrode. That is, for example, when the potential of the negative electrode falls below 0 V, lithium metal may be deposited on the surface of the negative electrode, and sufficient care must be taken when determining the charging conditions.
• a power storage device that can use a lithium electrode as a reference electrode can check the negative electrode potential during charging, so that the negative electrode potential does not fall below 0 V during the charging process. You can control it.
• lithium metal present on the lithium electrode is again applied with 0 V between the negative electrode terminal and the lithium electrode terminal by a potentiometer galvanostat, and the negative electrode is activated.
• Lithium ions can be supported again in an appropriate amount per unit weight of the substance, and the power storage device can be regenerated to its capacity before the high-temperature load test.
• a 0.5 mm thick phenolic resin molded plate is placed in a silicon knit electric furnace, and the temperature is raised to 500 ° C in a nitrogen atmosphere at a rate of 50 ° CZ for 50 ° C, and further to 650 ° C at a rate of 10 ° C for 7 hours. Then, heat treatment was performed to synthesize PAS.
• the PAS plate thus obtained was pulverized with a disk mill to obtain a PAS powder.
• the H / C ratio of this PAS powder was 0.22.
• a slurry was obtained by sufficiently mixing 100 parts by weight of the PAS powder and a solution of 10 parts by weight of poly (vinylidene fluoride) in 120 parts by weight of N-methylpyrrolidone.
• the slurry was applied on both surfaces of a copper expanded metal having a thickness of 40 m (porosity: 50%), dried, and pressed to obtain a 200 m PAS negative electrode. (Production method of positive electrode)
• a 0.5 mm thick phenolic resin molded plate is placed in a silicon knit electric furnace and heated up to 500 ° C in a nitrogen atmosphere at a rate of 5 O: / hour and further up to 650 ° C at a rate of 10 ° C / hour.
• PAS was synthesized.
• the PAS was activated with steam and then pulverized with a nylon pole mill to obtain a PAS powder.
• the specific surface area of the powder by the BET method was 1,500 m 2 Zg, and the HZC was 0.10 by elemental analysis.
• a slurry was obtained by sufficiently mixing 100 parts by weight of the above PAS powder and 100 parts by weight of polyvinylidene fluoride powder in 100 parts by weight of N-methylpyrrolidone.
• the slurry was coated with a carbon-based conductive paint to a thickness of 40 urn.
• the above positive electrode was cut into three pieces of 1.5 ⁇ 2.0 cm 2 size, one was used as a positive electrode, and the other was used as a negative electrode and a reference electrode.
• a simulated capacitor cell was assembled with a 50-m-thick nonwoven fabric made of paper as the separator and cathode.
• As the positive electrode electrolyte a solution obtained by dissolving triethylmethylammonium-tetrafluoroborate (TEMA'BF 4 ) at a concentration of 1 mol / 1 in propylene-ionate was used.
• the battery was charged to 2.5 V at a charging current of 10 mA, and then charged at a constant voltage. After a total charging time of 1 hour, the battery was discharged to 0 V at lmA.
• the capacitance per unit weight of the cell was found to be 21 F / g.
• the capacitance per unit weight of the positive electrode was determined from the potential difference between the reference electrode and the positive electrode to be 85 F / g.
• a PAS negative electrode with a thickness of 200 m and a PAS positive electrode with a thickness of 380 m are each 5.0 ⁇ 7.0 cm 2 in shape as shown in Fig. 15 (excluding terminal welds).
• the terminal welds of the positive electrode current collector and the negative electrode current collector are on opposite sides using a 25-thick cellulose-Z-rayon mixed nonwoven fabric as a separator.
• the positive electrode and the negative electrode were stacked such that the opposing surfaces of the negative electrode and the negative electrode had 10 layers.
• the electrode laminated unit 1 was obtained by ultrasonic welding to an aluminum positive electrode terminal and a nickel negative electrode terminal having a length of 5 Omm and a thickness of 0.1 mm. In addition, five positive electrodes were used and six negative electrodes were used. As shown in FIG. 1, two outer negative electrodes were formed by peeling one side of the negative electrode molded on both sides. The thickness is 120 m. The weight of the positive electrode active material is 1.7 times the weight of the negative electrode active material. (Preparation of electrode stack unit 2)
• PAS negative electrode having a thickness of 200 m, respectively PAS positive electrode having a thickness of 380 m in the first 6 Figure in shown Suyo shape, cut into 5.
• 0 X 8. 0 cm 2 (excluding the terminal welding parts) -
• the electrode stacking unit 2 was prepared in the same manner as the electrode stacking unit 1 except that the terminal welds of the positive electrode current collector and the negative electrode current collector were arranged on the same side as shown in FIG. Obtained.
• lithium metal foil 160 mm, 5.0 x 7.0 cm 2
• a stainless steel sheet with a thickness of 80 im was used.
• one sheet was placed on top of the electrode stack unit 1 so as to face the negative electrode to obtain a three-electrode stack unit.
• a 10mm wide, 50mm long, 0.1mm thick nickel lithium electrode terminal was ultrasonically welded to the terminal weld (1 piece) of the lithium electrode current collector, as shown in Fig. 1. They were arranged in the same direction as the positive terminal.
• the above three-electrode laminated unit is placed inside a deep drawn outer film, covered with an outer laminating film, and three sides are fused. After that, ethylene carbonate, ethyl carbonate and propylene carbonate are used as electrolytes in a weight ratio of 3: 4. : 1 and the mixed solvent, after the solution of L i PF 6 to a concentration of 1 mol 1 was vacuum impregnated, fused the rest one side, the evening film type Capacity assembly 8 cells. Immediately after assembly, the negative electrode terminal and the lithium electrode terminal were short-circuited.
• a lithium metal foil 160 m, 5.0 x 8.0 cm 2
• a stainless steel net 80 m in thickness and used as a lithium electrode, facing the negative electrode.
• One electrode was placed on the upper part of the electrode stack unit 2 to obtain a three-electrode stack unit.
• the directions of the positive electrode, the negative electrode and the lithium electrode terminal were the same as shown in FIG.
• the above triode laminated unit is installed inside a deep drawn outer film, 8 cells of a film capacitor were assembled in the same manner as cell 1. Immediately after assembly, the negative electrode terminal and the lithium electrode terminal were short-circuited.
• the terminal weld of the lithium current collector (1 piece) and the terminal weld of the negative electrode current collector (6 pieces) were ultrasonically welded to short-circuit the negative electrode and lithium electrode inside the cell.
• An eight-cell film-type capacitor was assembled in the same manner as for cell 1, except that a nickel negative electrode terminal having a width of 10 mm, a length of 50 mm, and a thickness of 0.1 mm was ultrasonically welded.
• each cell was disassembled one by one.Since the lithium metal in the cell 3 was completely lost, the static electricity of 65 FZ g per unit weight of the negative electrode active material was reduced. It was determined that lithium for obtaining electric capacity was precharged. The remaining cells 1, 2, 4, and 5 had lithium metal remaining.
• the rate of carrying lithium could be increased by applying a negative voltage between the negative electrode terminal and the lithium terminal.
• the applied negative voltage is too large, lithium will deposit on the negative electrode surface. Care must be taken, as it may occur.
• the filling rate of the active material changes depending on how the terminals are selected, and the capacity and energy density differ. It is desirable that the terminals be in the same direction as in cell 2 or cell 5 because of higher capacity.
• cells 1, 2, and 3 carrying lithium through an external circuit have smooth cell surfaces and low DC internal resistance, while cells 4 and 5 short-circuited inside the cell are warped and distorted.
• the average cell thickness was thicker than cells 1, 2, and 3.
• the distortion of the electrode edge tends to increase.
• the DC internal resistance is The result was greater than 3.
• Example 2 Six cells were assembled in the same manner as in Example 1 except that lithium was not supported on the negative electrode. Each of the above 6 cells was charged at a constant current of 1000 mA until the cell voltage reached 3.3 V, and then a constant current constant voltage charge of applying a 3.3 V constant voltage was performed for 1 hour. Next, discharging was performed at a constant current of 100 mA until the cell voltage reached 1.6 V. This 3.3 V-1.6 V cycle was repeated, and the cell capacity was evaluated in the third discharge. The result was 3 OmAh (average value of 6 cells). The energy density at this capacity was 4.5 Wh / l, less than 1 OWhZ1. When lithium was not supported on the negative electrode, sufficient capacity could not be obtained.
• Example 2 Seven cells were assembled in the same manner as in Example 1 except that a 20 m-thick aluminum foil was used for the positive electrode current collector and a 20 tm-thick copper foil was used for the negative electrode current collector. Immediately after assembly, the negative electrode terminal and the lithium electrode terminal were short-circuited. After leaving at room temperature for 20 days, one cell was decomposed, and almost all of the lithium metal remained.
• the remaining six cells were charged at a constant current of 100 OmA until the battery voltage reached 3.3 V, and then a constant current constant voltage charge of applying a 3.3 V constant voltage was performed for 1 hour. Then, discharging was performed at a constant current of 10 OmA until the cell voltage reached 1.6 V. This 3.3 V-1.6 V cycle was repeated, and the cell capacity was evaluated at the third discharge. The result was 32 mAh (average value of 6 cells). The energy density at this capacity was 4.8 Wh / l, less than 1 OWh / 1.
• Example 7 Seven cells were assembled in the same manner as in Example 1 except that a lithium metal foil of 320 m was used as a lithium electrode. After assembly, apply a voltage of 0 V between the negative electrode and the lithium electrode under a constant voltage condition using a potentiogalvanostat (Hokuto Denko Co., Ltd., HA-301), and apply a current between the negative electrode and the lithium electrode. Coulomb / ampere hour Accumulation with a meter (Hokuto Denko Co., Ltd., HF-201), and when the integrated current reaches 40 OmAhZg per unit weight of the negative electrode active material, the loading of lithium is terminated, so that the unit weight of the negative electrode active material is reduced.
• a potentiogalvanostat Hokuto Denko Co., Ltd., HA-301
• the lithium was precharged to obtain a capacitance of 650 F / g. After preliminarily charging lithium, one cell was disassembled, and it was confirmed that a lithium metal foil of about half of the initial thickness remained. When the potential difference between the negative electrode and the lithium electrode of the remaining six cells was measured, they were all at 0.25 V, and it was confirmed that lithium was precharged similarly in all six cells.
• the remaining 6 cells were charged with a constant current of 100 OmA until the cell voltage reached 3.3 V, and then a constant current constant voltage charge of applying a 3.3 V constant voltage was performed for 1 hour. Then, discharging was performed at a constant current of 10 OmA until the cell voltage reached 1.6 V. This 3.3 V-1.6 V cycle was repeated, and the cell capacity was evaluated at the third discharge. The result was 91 mAh (average value of 6 cells). The energy density at this capacity was 15 WhZl.
• a lithium electrode similar to the lithium electrode using a 160-m lithium metal foil was arranged below the electrode stacking unit 1, and 7 cells were assembled in the same manner as in Example 1 except that the lithium electrode was used as a reference electrode.
• the terminal of the reference electrode was arranged so as to be in the same direction as the negative electrode terminal, opposite to the lithium electrode. Immediately after assembly, short-circuit the negative terminal and lithium terminal. I let you.
• the remaining six cells were charged with a constant current of 100 OmA until the cell voltage reached 3.3 V, and then a constant current constant voltage charge of applying a 3.3 V constant voltage was performed for 1 hour. Then, discharging was performed at a constant current of 100 mA until the cell voltage reached 1.6 V. This 3.3 V-1.6 V cycle was repeated, and the cell capacity was evaluated at the third discharge. The result was 9 ImAh (average value of 6 cells). The energy density at this capacity was 15 WhZ1.
• a power storage device having a reference electrode as in this embodiment is preferable because the negative electrode potential during charging can be checked, but as in Embodiment 4, the lithium electrode has a larger amount of lithium than is required for preliminary charging in the lithium electrode. is disposed of lithium, t example 6 better to use lithium metal remaining after the preliminary charging end as a reference electrode is convenient suitable as configuration of the cell
• the 6 cells whose capacity was measured in Example 4 were charged at a constant current of 1000 mA each until the cell voltage reached 3.3 V, and then the 6 cells were transferred into a 60 ° C constant temperature bath to transfer 3.3 V to a voltage of 3.3 V.
• a high-temperature load test in which voltage was continuously applied for 2000 hours was performed. After the test was completed, the cell capacity was evaluated in the same manner as the capacity measurement after cell assembly, and was 82 mAh (average value of 6 cells).
• 0 V is applied between the negative electrode terminal and the lithium electrode terminal using a potentiogalvanostat, and the flowing current is calculated using a coulomb meter.
• the integrated current is 5 OmAhZg per unit weight of the negative electrode active material. When it becomes When the loading of lithium was stopped and the same cell capacity was measured, the capacity returned to 9 lmA (average value of 6 cells), which was the capacity before the high-temperature load test.
• the usage method in which appropriate lithium is subsequently supplied from the lithium electrode to the power storage device having deteriorated characteristics as in this embodiment is suitable for extending the life of the power storage device.
• a slurry was obtained by thorough mixing. The slurry was applied to both sides of a carbon-based conductive paint-coated aluminum expanded metal having a thickness of 40 m (porosity: 50%) and an aluminum foil having a thickness of 20 m, dried and pressed. It was obtained o 0 2 positive electrode 1 and 2.
• a PAS negative electrode was obtained in the same manner as in the method for producing the negative electrode of Example 1, except that the copper expanded metal having a thickness of 40 xm (porosity: 50%) was replaced with a copper foil of 20 im.
• the positive electrode current collector and the negative electrode current collector were placed on the opposite sides as shown in Fig. 15
• the positive electrode and the negative electrode were laminated so that the opposing surfaces became 10 layers.
• Each of the positive electrode current collector and the negative electrode current collector has a hole penetrating the front and back surfaces.
• the uppermost and lowermost parts are arranged with a separator and taped on four sides.
• the terminal welds of the positive electrode current collector (5 pieces) and the terminal welds of the negative electrode current collector (6 pieces) are each 20 mm wide. Ultrasonic welding was performed on an aluminum positive electrode terminal and a nickel negative electrode terminal having a length of 50 mm and a thickness of 0.1 mm to obtain an electrode laminated unit 3.
• a lithium metal foil (220 ⁇ , 5.0 X 7.0 cm 2 ) was used as a lithium electrode on the exterior film that had been deep drawn by 3.5 mm, and a stainless steel mesh with a thickness of 80 / m was used.
• One was placed above the electrode stack unit 3 so as to face the negative electrode, and a three-electrode stack unit was obtained.
• the terminal welding part of the lithium electrode current collector One (1) was ultrasonically welded with a nickel-made lithium electrode terminal with a width of 10 mm, a length of 50 mm, and a thickness of 1 mm, and placed in the same direction as the positive electrode terminal as shown in Fig. 1.
• the three-electrode laminated unit is placed inside a deep-drawn exterior film, covered with an exterior laminating film and fused on three sides, and then ethylene carbonate, ethyl carbonate and propylene carbonate are used as electrolytes in a weight ratio of 3: 4: 1. and in the mixed solvent, after 1 mol / 1 concentration in to the solution vacuum impregnated with dissolving the L i PF 6, by fusing the remaining side was assembled evening film type Capacity 1 cells. After assembly, apply 0 V between the negative electrode terminal and the lithium electrode terminal with a potentiogal vanostat, accumulate the flowing current with a coulomb / ampere hour meter, and calculate the accumulated current per unit weight of the negative electrode active material. Preliminary charging was carried out by terminating the loading of lithium at 30 OmAhZg.
• the lithium carrying PAS negative electrode (six sheets) and assembled the L i C O_ ⁇ 2 positive electrode 2 (five sheets) film type Capacity evening one cell like the creation of the cell 6, except that Ru used.
• the lithium secondary battery was not precharged after assembly.
• both the positive electrode current collector and the negative electrode current collector use foils without holes.
• the discharge potential of the LiCoO 2 positive electrode has a flat portion near 3.8 V which does not change with time.
• the positive electrode potential of cell 6 a flat portion near 3.8 V with no change over time could be measured, but cell 7 could not be measured. This is thought to be because the mesh for the current collector can measure not only the potential near the lithium electrode, but also the electrode potential inside the stacked unit, rather than using foil for the positive and negative electrode current collectors. .
• the power storage device of the present invention is a power storage device including a positive electrode, a negative electrode, and a lithium electrode that can be connected to an external circuit, and an electrolyte that fills a gap between the respective electrodes.
• the lithium electrode is connected to the lithium electrode and the negative electrode through an external circuit.
• lithium can be supplied to the negative electrode, causing uneven loading of lithium on the negative electrode, deformation of the cell, and dissolution of the electrolyte in a state where the cell is not completely sealed. Problems such as temperature rise can be easily solved, and the service life of the cell can be prolonged.
• the lithium electrode as the reference electrode, the states of the positive electrode and the negative electrode can be individually grasped.
• the power storage device of the present invention having such characteristics can be suitably used for a film-type lithium ion secondary battery, a capacitor, and the like.

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• 2003
  • 2003-12-25 KR KR1020057012133A patent/KR100874199B1/ko active IP Right Grant
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